CN116446032A - Small particle precursor for single crystal and preparation method thereof - Google Patents
Small particle precursor for single crystal and preparation method thereof Download PDFInfo
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- CN116446032A CN116446032A CN202310357155.XA CN202310357155A CN116446032A CN 116446032 A CN116446032 A CN 116446032A CN 202310357155 A CN202310357155 A CN 202310357155A CN 116446032 A CN116446032 A CN 116446032A
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- 239000002245 particle Substances 0.000 title claims abstract description 50
- 239000002243 precursor Substances 0.000 title claims abstract description 40
- 239000013078 crystal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000000243 solution Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011164 primary particle Substances 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 23
- 230000006911 nucleation Effects 0.000 claims abstract description 22
- 238000010899 nucleation Methods 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000012716 precipitator Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 20
- 230000001276 controlling effect Effects 0.000 claims description 19
- 230000007704 transition Effects 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 9
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 9
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 9
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- KTOXGWMDJYFBKK-UHFFFAOYSA-L manganese(2+);diacetate;dihydrate Chemical compound O.O.[Mn+2].CC([O-])=O.CC([O-])=O KTOXGWMDJYFBKK-UHFFFAOYSA-L 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 102220043159 rs587780996 Human genes 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 15
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 239000011362 coarse particle Substances 0.000 abstract description 4
- 239000010419 fine particle Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005086 pumping Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a monocrystal small particle precursor with a primary particle morphology by mixing coarse particles and fine particles. The method comprises the steps of adding a certain proportion of salt solution, a precipitator a and a complexing agent b into a base solution containing the precipitator and the complexing agent, and controlling the pH value in a reaction system to be in linear periodical change of firstly rising and then reducing within a certain range after finishing a nucleation stage until the particle size of precursor particles reaches a target particle size. And carrying out solid-liquid separation, washing and drying on the obtained product to finally prepare the ternary precursor particles with the surface morphology in a coarse-fine mixed state. When the precursor particles with the morphology of the precursor particles are subjected to single crystal sintering, the sintering temperature can be reduced, the production cost is saved, the lithium nickel mixed discharge level is reduced, meanwhile, the sintered single crystal has proper single crystal particle size, no additional melting aid or melting inhibitor is needed to be introduced to control the single crystal particle size, and excellent capacity performance and cycle advantages are shown.
Description
Technical Field
The invention belongs to the technical field of preparation of ternary precursor materials of lithium ion batteries, and particularly relates to a preparation method of a small particle precursor for single crystals.
Background
The ternary positive electrode material of the lithium ion battery has been widely applied to the field of power batteries at present due to higher energy density, better cycle stability and better environmental friendliness.
Along with the gradual improvement of the requirements of the continuous voyage mileage of the automobile, the ternary cathode material of the lithium ion battery gradually moves from medium-low nickel to high nickel, and the energy density of the system is improved through the improved nickel content, so that the long continuous voyage requirement is met. However, as the nickel content is increased, the phase change of the polycrystalline material is serious, and the cycle performance and the safety performance are gradually reduced, so that the material is changed from polycrystalline to monocrystalline, the monocrystalline material has higher cut-off voltage, higher capacity is shown under the same nickel content, the cycle performance and the safety performance are better, and the polycrystalline material is gradually applied to the field of power batteries at present.
However, the sintering temperature of the monocrystalline material is too high, which makes the size of the monocrystalline particles difficult to control after sintering, the capacity is low due to the oversized particles, and the cycle performance is reduced due to the undersize particles; on the other hand, the higher the sintering temperature is, the more lithium nickel is mixed, and the reversible capacity is reduced.
Therefore, how to ensure that the single crystal positive electrode has proper single crystal grain size and low lithium nickel mixing degree becomes a difficult problem for material development.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a small particle precursor for single crystals, which is formed by mixing coarse particles with fine particles. Based on the coprecipitation principle and the agglomeration growth of the precursor, after the nucleation stage and the transition stage are completed, the pH of the system is controlled to periodically and linearly change in a certain interval, the supersaturation degree of the linear reciprocating change is provided for the reaction system, the precursor hexagonal wafers are dynamically combined into finer primary particles and coarser primary particles under the condition of the changing supersaturation degree, and the precursor particles with certain granularity and the surface with coarse-fine mixed morphology are finally formed along with the growth of the particles.
On one hand, the invention provides a preparation method of a small particle precursor for single crystals, which is characterized in that the small particle precursor is prepared by mixing coarse particles with fine particles and has the shape of primary particles, and the preparation method comprises the following steps:
(1) And (3) a nucleation stage: adding a metal salt solution, a precipitator a and a complexing agent b into a base solution containing pure water, the precipitator a and the complexing agent b, and controlling a reaction system to be in a certain time T 1 Internal pH 1 The method is constant and completes the nucleation stage;
(2) And (3) a transition stage: pH at the stage of nucleation 1 At a certain time T 2 Gradually decreasing the internal linearity to pH 2 Completing a transition stage;
(3) Period fluctuation phase of supersaturation degree: the adding amount of the precipitant is regulated and controlled, the pH value of the reaction system is controlled to periodically fluctuate by taking T as a period and pH-L as a lower limit and pH-H as an upper limit, so that the periodic fluctuation of supersaturation degree is realized, and the reaction is stopped until precursor particles grow to the target particle size;
(4) And (3) separating, washing and drying the product obtained in the step (3) to obtain the monocrystal small particle precursor with the morphology of coarse and fine mixed primary particles.
In the step (1) of the present invention, the precipitant a is one or more selected from aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably aqueous sodium hydroxide.
As a preferred embodiment, in the step (1) of the present invention, the concentration C of the precipitant a 1 5-20mol/L.
In the step (1), the complexing agent b is selected from one or more of ammonia water, ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium acetate aqueous solution, preferably ammonia water solution.
As a preferable mode, in the step (1) of the present inventionConcentration C of complexing agent b 2 0.1 to 5mol/L.
As a preferable mode, in the step (1) of the present invention, the complexing agent concentration C of the base solution containing pure water and the precipitants a, b is set before the reaction is started 3 0.1 to 9mol/L.
As a preferred embodiment, in the step (1) of the present invention, the pH is set at a value before the initiation of the reaction 1 11.50 to 12.20.
As a preferable mode, in the step (1) of the present invention, the T 1 15 min-120 min.
As a preferable scheme, in the step (1), the metal salt solution contains three elements of nickel, cobalt and manganese, and the total concentration of the three metal elements is 0.1-4 mol/L. As a preferable scheme, the molar percentages of nickel, cobalt and manganese elements in the metal salt solution are respectively a, b and c, wherein a is more than or equal to 50% and less than or equal to 90%, b is more than or equal to 5% and less than or equal to 30%, and c is more than or equal to 5% and less than or equal to 20%.
As a preferred embodiment, the source of the nickel, cobalt and manganese elements in the metal salt solution according to the present invention is hydrochloride, acetate, sulfate or hydrate thereof of the corresponding metal element, and other materials known in the art, and suitable examples include, but are not limited to, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate dihydrate, and the like.
As a preferable mode, in the step (2) of the present invention, the pH is 2 10.00-10.50.
As a preferable mode, in the step (2) of the present invention, the T 2 2 to 6 hours.
As a preferable embodiment, in the step (3) of the present invention, the lower limit pH-L=pH 2 The upper limit pH value-H is 10.80-11.40, the period T is 30-120 min, and the number of periodic fluctuation is 20-200.
In a preferred embodiment, in the step (4) of the present invention, the separation may be performed by any method known in the art, and preferably, a centrifuge is used.
As a preferred embodiment, in the step (4), the washing is performed with deionized water until the pH of the washing supernatant is neutral.
In a preferred embodiment, in the step (4), the drying temperature is 100-150 ℃ and the drying time is 48-60 h.
On the other hand, the invention also provides a small particle precursor for single crystals, which is prepared by the method, and has the chemical formula of Ni 1-x-y Co x Mn y (OH) 2 Wherein 0.5-x-y is less than or equal to 1 and less than or equal to 0.9, x is less than or equal to 0.05 and less than or equal to 0.3,0.05, y is less than or equal to 0.2, and the particles D50=3-4 mu m. .
The method has the advantages that the overall supersaturation level of the system is accurately regulated and controlled through a pH control strategy, so that precursor hexagonal nano sheets are combined into primary particles with different thicknesses in a bonding mode, the surface of a final precursor product is in the shape of primary particles with mixed thicknesses, when single crystal sintering is carried out on the precursor particles with the shape, the sintering temperature can be reduced, the production cost is saved, the lithium nickel mixed discharge level is reduced, meanwhile, the sintered single crystal has proper single crystal particle size, no additional melting aid or melting inhibitor is needed to control the single crystal particle size, the mutual balance of capacity and circulation is achieved, and excellent electrochemical performance is shown.
Drawings
FIG. 1 is a SEM image of a precursor of morphology of coarse and fine particles prepared according to example 1 of the method of the invention
FIG. 2 is an SEM spectrum of a precursor of a coarser primary particle morphology prepared in comparative example 1 of the method of the invention
FIG. 3 is an SEM spectrum of a precursor of finer primary particle morphology prepared in comparative example 2 of the present invention
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The main raw materials used in the examples and comparative examples are as follows:
the characterization methods used in the examples and comparative examples are as follows:
the particle size testing instrument is a Master sizer 3000 particle size analyzer, and the testing method refers to national standard GB/T19077-2016.
The instrument used for SEM testing was Phenom Pro, and the test was imaged using secondary electron mode.
Example 1
Ni is prepared in this example 0.9 Co 0.05 Mn 0.05 (OH) 2 The primary particles are in a coarse-fine mixed morphology, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 12.10 (prepared by sodium hydroxide), ammonia concentration of 0.2mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 12.20 within a certain period of 45min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.50 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) Period fluctuation phase of supersaturation degree: and (3) controlling the pH value of the reaction system to periodically fluctuate with 45min as a period, 10.50 as a lower limit and 11.40 as an upper limit by regulating and controlling the adding amount of the sodium hydroxide solution, and periodically fluctuating the supersaturation degree by taking 30min as a period until precursor particles grow to 3.5 mu m, and stopping the reaction.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was fired into single crystals at 800℃with an average single crystal grain size of 2 μm, a discharge capacity of 203mAh/g at 0.33C rate for the button cell half cell, and a capacity retention rate of 91.8% at 1C rate for 100 cycles. The firing temperature is lower, the lithium nickel mixed discharge degree is lower, the cost is low, the single crystal size is proper, and the ultrahigh discharge capacity and the excellent cycle performance are shown.
Example 2
Ni is prepared in this example 0.9 Co 0.05 Mn 0.05 (OH) 2 The primary particles are in a coarse-fine mixed morphology, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 12.10 (prepared by sodium hydroxide), ammonia concentration of 0.2mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 12.20 within a certain period of 45min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.50 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) Period fluctuation phase of supersaturation degree: and (3) controlling the pH value of the reaction system to periodically fluctuate with 45min as a period, 10.50 as a lower limit and 11.40 as an upper limit by regulating and controlling the adding amount of the sodium hydroxide solution, and periodically fluctuating the supersaturation degree by 60min until precursor particles grow to 3.5 mu m, and stopping the reaction.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was fired into single crystals at 800℃with an average single crystal grain size of 1.97 μm, a discharge capacity of 202.5mAh/g at 0.33C rate for the button cell half cell, and a capacity retention rate of 91.5% at 1C rate for 100 cycles. The firing temperature is lower, the lithium nickel mixed discharge degree is lower, the cost is low, the single crystal size is proper, and the ultrahigh discharge capacity and the excellent cycle performance are shown.
Example 3
Ni is prepared in this example 0.9 Co 0.05 Mn 0.05 (OH) 2 The primary particles are in a coarse-fine mixed morphology, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 12.10 (prepared by sodium hydroxide), ammonia concentration of 0.2mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 12.20 within a certain period of 45min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.50 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) Period fluctuation phase of supersaturation degree: and (3) controlling the pH value of the reaction system to periodically fluctuate with 45min as a period, 10.50 as a lower limit and 11.40 as an upper limit by regulating and controlling the adding amount of the sodium hydroxide solution, and periodically fluctuating the supersaturation degree until precursor particles grow to 3.5 mu m, and stopping the reaction.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was fired into single crystals at 800℃with an average single crystal grain size of 2.05 μm, a discharge capacity of 202.6mAh/g at 0.33C rate for the button cell half cell, and a capacity retention rate of 90.9% at 1C rate for 100 cycles. The firing temperature is lower, the lithium nickel mixed discharge degree is lower, the cost is low, the single crystal size is proper, and the ultrahigh discharge capacity and the excellent cycle performance are shown.
Example 4
Ni is prepared in this example 0.5 Co 0.3 Mn 0.2 (OH) 2 The primary particles are in a coarse-fine mixed morphology, and the preparation method comprises the following steps:
respectively preparing a sodium hydroxide solution with the concentration of 4mol/L as a precipitator, an ammonia water solution with the concentration of 13mol/L as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution with the concentration of 2mol/L (Ni: co: mn=5:3:2) with the same volume. Preparing alkaline base solution with pH of 11.50 (prepared by sodium hydroxide), ammonia concentration of 0.1mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 11.50 within a certain period of 60min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.00 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) Period fluctuation phase of supersaturation degree: and (3) controlling the pH value of the reaction system to periodically fluctuate with 45min as a period, 10.00 as a lower limit and 10.80 as an upper limit by regulating and controlling the adding amount of the sodium hydroxide solution, and periodically fluctuating the supersaturation degree until precursor particles grow to 3.5 mu m, and stopping the reaction.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.5 Co 0.3 Mn 0.2 (OH) 2 。
The sample was fired into single crystals at 900℃with an average single crystal grain size of 2.11 μm, a discharge capacity of 163mAh/g at 0.33C rate for the button cell half cell, and a capacity retention of 93.8% at 1C rate for 100 cycles. The firing temperature is lower, the lithium nickel mixed discharge degree is lower, the cost is low, the single crystal size is proper, and the ultrahigh discharge capacity and the excellent cycle performance are shown.
Example 5
Ni is prepared in this example 0.7 Co 0.1 Mn 0.2 (OH) 2 The primary particles are in a coarse-fine mixed morphology, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 11.85 (prepared by sodium hydroxide), ammonia concentration of 0.15mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 11.85 within 30min for a certain time to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.25 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) Period fluctuation phase of supersaturation degree: and (3) controlling the pH value of the reaction system to periodically fluctuate with 45min as a period, 10.25 as a lower limit and 11.10 as an upper limit by regulating and controlling the adding amount of the sodium hydroxide solution, and periodically fluctuating the supersaturation degree by 120min until precursor particles grow to 3.5 mu m, and stopping the reaction.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was sintered into single crystals at 850℃with an average single crystal grain size of 2.06 μm, a discharge capacity of 184mAh/g at 0.33C rate for the button cell half cell, and a capacity retention rate of 92.1% at 1C rate for 100 cycles. The firing temperature is lower, the lithium nickel mixed discharge degree is lower, the cost is low, the single crystal size is proper, and the ultrahigh discharge capacity and the excellent cycle performance are shown.
Comparative example 1
Manufactured by this exampleIs prepared from Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 The primary particle shape is thicker, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 12.20 (prepared by sodium hydroxide), ammonia concentration of 0.2mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 12.20 within a certain period of 45min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 11.40 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) And (3) a growth stage: the pH and ammonia concentration of the system were maintained stable until the particle D50 grew to 3.5 μm and the reaction was completed.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with coarser primary particle morphology 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was fired into single crystals at 790℃with a corresponding average single crystal grain size of 2.6. Mu.m, a discharge capacity of 192.7mAh/g at 0.33C rate for the button cell half cell and a capacity retention of 91% at 1C rate for 100 cycles. The firing temperature was lowest but resulted in an oversized single crystal, resulting in a longer lithium ion migration path, a capacity of 11.3 g lower than that of example one, and cycle performance comparable to that of example one.
Comparative example 2
Ni is prepared in this example 0.9 Co 0.05 Mn 0.05 (OH) 2 The primary particle shape is finer, and the preparation method comprises the following steps:
respectively preparing 4mol/L sodium hydroxide solution as a precipitator, and 13mol/L ammonia water solution as a complexing agent, and dissolving nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate in deionized water to prepare a metal salt solution (Ni: co: mn=9:0.5:0.5) with the same volume and 2 mol/L. Preparing alkaline base solution with pH of 12.20 (prepared by sodium hydroxide), ammonia concentration of 0.2mol/L and volume of 20L in a reaction kettle, continuously introducing nitrogen for 20min to remove dissolved oxygen of the base solution, keeping the reaction kettle sealed and slightly positive pressure, and protecting the reaction kettle by inert gas in the whole process. The temperature of the reaction system is maintained at 50 ℃ by heating in a water bath, and the stirring speed is 600rpm.
(1) And (3) a nucleation stage: and continuously pumping 2mol/L of metal salt solution, 4mol/L of sodium hydroxide solution and 13mol/L of ammonia water solution into the reaction kettle at a certain rate by using a metering pump, and controlling the pH of the reaction system to be kept constant at 12.20 within a certain period of 45min to finish the nucleation stage.
(2) And (3) a transition stage: the pH of the system is linearly reduced to 10.50 within 90min by reducing the flow of the alkali liquor, so that the transition stage is completed.
(3) And (3) a growth stage: the pH and ammonia concentration of the system were maintained stable until the particle D50 grew to 3.5 μm and the reaction stopped.
(4) After the reaction is finished, pumping the slurry in the kettle into a centrifuge through a diaphragm pump to realize solid-liquid separation, and washing for 2 hours by using deionized water until the washing clear liquid is developed to be neutral in pH test paper. Then transferring to an oven, and continuing for 50 hours at 100 ℃ to obtain a small particle precursor Ni with the morphology of coarse and fine mixed primary particles 0.9 Co 0.05 Mn 0.05 (OH) 2 。
The sample was fired into single crystals at 830℃with an average single crystal grain size of 1.4. Mu.m, a discharge capacity of 199.5mAh/g at 0.33C rate for the button cell half cell and a capacity retention of 78% at 1C rate for 100 cycles. The sintering temperature is too high, so that the cost is high, the lithium nickel mixed emission degree is high, the single crystal size is small, the capacity advantage cannot be displayed, and the cycle performance is greatly reduced.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. A method for preparing a small particle precursor for single crystals, comprising the steps of:
(1) And (3) a nucleation stage: adding a metal salt solution, a precipitator a and a complexing agent b into a base solution containing the precipitator and the complexing agent, and controlling a reaction system to be in a certain time T 1 Internal pH 1 The method is constant and completes the nucleation stage;
(2) And (3) a transition stage: pH at the stage of nucleation 1 At a certain time T 2 Gradually decreasing the internal linearity to pH 2 Completing a transition stage;
(3) Period fluctuation phase of supersaturation degree: the adding amount of the precipitant is regulated and controlled, the pH value of the reaction system is controlled to periodically fluctuate by taking T as a period and pH-L as a lower limit and pH-H as an upper limit, so that the periodic fluctuation of supersaturation degree is realized, and the reaction is stopped until precursor particles grow to the target particle size;
(4) And (3) separating, washing and drying the product obtained in the step (3) to obtain the monocrystal small particle precursor with the morphology of coarse and fine mixed primary particles.
2. The process according to claim 1, wherein in step (1), the precipitant a is selected from one or more of aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, preferably aqueous sodium hydroxide; and/or the concentration C of the precipitant a 1 5-20mol/L.
3. The process according to claim 1 or 2, wherein the complexing agent b is selected from the group consisting of ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetateOne or more of the aqueous solutions, preferably an aqueous ammonia solution; and/or the concentration C of the complexing agent b 2 0.1 to 5mol/L.
4. A process according to any one of claims 1 to 3, wherein in step (1), the complexing agent concentration C of the base solution containing pure water and precipitants a, b is at a concentration C before the reaction is initiated 3 0.1 to 9mol/L; and/or, before the reaction is initiated, the pH 1 11.50 to 12.20, the T 1 15 min-120 min.
5. The method according to any one of claims 1 to 4, wherein in the step (1), the metal salt solution contains three elements of nickel, cobalt and manganese, and the total concentration of the three metal elements is 0.1 to 4mol/L; and/or the molar percentage of nickel, cobalt and manganese elements in the metal salt solution is a, b and c respectively, wherein a is more than or equal to 50% and less than or equal to 90%, b is more than or equal to 5% and less than or equal to 30%, and c is more than or equal to 5 and less than or equal to 20%.
6. The method according to any one of claims 1 to 5, wherein the source of the nickel, cobalt and manganese elements in the metal salt solution is the hydrochloride, acetate, sulfate or hydrate thereof of the corresponding metal element; such as nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate, nickel acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate dihydrate.
7. The method according to any one of claims 1 to 6, wherein in the step (2), the pH is as follows 2 10.00 to 10.50; the T is 2 2 to 6 hours.
8. The process according to any one of claims 1 to 7, wherein in step (3), the lower limit pH-l=ph 2 The upper limit pH value-H is 10.80-11.40, the period T is 30-120 min, and the number of periodic fluctuation is 20-200.
9. The method of any one of claims 1 to 8, wherein the drying is carried out at a temperature of 100 to 150 ℃ for a period of 48 to 60 hours.
10. The small particle precursor for single crystals prepared by the preparation method as set forth in any one of claims 1 to 9, having the chemical formula of Ni 1-x-y Co x Mn y (OH) 2 Wherein 0.5-x-y is less than or equal to 1 and less than or equal to 0.9, x is less than or equal to 0.05 and less than or equal to 0.3,0.05, y is less than or equal to 0.2, and the particles D50=3-4 mu m.
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